Different from the conventional mono-metal catalysts, tungsten-cobalt intermetallic compound W₆Co₇, which belongs to monoclinic crystal system, presents lower structural symmetry and a very unique atomic arrangement. Therefore, W₆Co₇ exhibits specific geometry match towards the end structures of single-walled carbon nanotubes (SWNTs). This kind of one-by-one recognition between a crystal plane to a certain chirality of SWNTs enables this tungsten-based intermetallic compound an efficient template for structure-specified growth of SWNTs. This idea was revealed by both DFT simulation and the result of chemical vapor deposition growth of SWNTs. The manipulation of the structures of the W₆Co₇ catalysts was also performed to meet the requirements of the selective growth of SWNTs with different chiralities.